EP3187264B1 - Hydrogenation catalyst and manufacturing method therefor - Google Patents
Hydrogenation catalyst and manufacturing method therefor Download PDFInfo
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- EP3187264B1 EP3187264B1 EP15836244.2A EP15836244A EP3187264B1 EP 3187264 B1 EP3187264 B1 EP 3187264B1 EP 15836244 A EP15836244 A EP 15836244A EP 3187264 B1 EP3187264 B1 EP 3187264B1
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- noble metal
- hydrogenation catalyst
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- aqueous solution
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- 238000005984 hydrogenation reaction Methods 0.000 title claims description 94
- 239000003054 catalyst Substances 0.000 title claims description 86
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 68
- 229910000510 noble metal Inorganic materials 0.000 claims description 68
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 43
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 25
- 239000002082 metal nanoparticle Substances 0.000 claims description 24
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 229910001453 nickel ion Inorganic materials 0.000 claims description 22
- 239000003638 chemical reducing agent Substances 0.000 claims description 21
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- -1 palladium ions Chemical class 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 239000001509 sodium citrate Substances 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 11
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 150000004687 hexahydrates Chemical class 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- 239000002070 nanowire Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000004438 BET method Methods 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229910003603 H2PdCl4 Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZXVOCOLRQJZVBW-UHFFFAOYSA-N azane;ethanol Chemical compound N.CCO ZXVOCOLRQJZVBW-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- B01J35/23—
-
- B01J35/33—
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- B01J35/393—
-
- B01J35/612—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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- B01J35/58—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates to a hydrogenation catalyst and a method of manufacturing the hydrogen catalyst, and more particularly to a hydrogenation catalyst with magnetism and a method of manufacturing the same.
- metal catalysts are frequently used in the hydrogenation system of aromatic compounds. Compared with other catalytic reactions using non-metallic catalysts, metal catalysts are not only clean but also have a low impact on the economy and the environment. In addition, noble metals such as palladium, ruthenium, rhodium, and platinum have been demonstrated to have high catalytic activities in a hydrogen atmosphere.
- a noble metal such as platinum (Pt) and palladium (Pd)
- Pt platinum
- Pd palladium
- SiO 2 and Al 2 O 3 as a catalyst carrier
- cyclohexane as a solvent to carry out the hydrogenation reaction of polystyrene.
- the hydrogenation reaction of polystyrene catalyzed by Pt/SiO 2 catalyst at a pressure of 875 bar, and a temperature of 150 °C can obtain a hydrogenation rate of 98.4%.
- a hydrogenation rate approaches 100% under a pressure of 100 bar at a temperature of 200 °C.
- the China Patent No. 101815575 issued on 2010 for Bayer Corporation mentioned that the catalyst used in the gas phase reaction can catalyze the hydrogenation of nitrobenzene to become aniline.
- the method includes steps of mixing 106.4 mg palladium chloride (PdCl 2 ), 6 ml hydrochloric acid (HCl), and 294 ml distilled water to obtain 300 ml palladium chloride acid (H 2 PdCl 4 ).
- step (a) the mixed solution of 15 ml H 2 PdCl 4 and 31.5 ml water and 3.5 ml methanol was added 33.25 mg polyvinylpyrrolidone
- step (b) 0.6 ml tetraethoxysilane (TEOS) was mixed with 7 ml ethanol. Subsequently, the mixed solution in step (a) was stirred violently, and a mixture of ethanol-ammonia (NH 3 ) was added therein, then the mixture of ethanol-TEOS was quickly added therein, too. After stirring overnight at room temperature, the precipitation was washed with ethanol, and Pd-SiO 2 nanoparticles were obtained by centrifugation. In step (c), 0.43 g alcohol-polyethylene glycol ether (such as Marlipal) was dissolved in water to prepare an aqueous solution of Marlipal.
- TEOS tetraethoxysilane
- step (b) the Pd-SiO 2 nanoparticles obtained in step (b) were dispersed in 40 g ethanol and heated to 30 °C. Subsequently, the aqueous solution of Marlipal was added to 30 °C Pd-SiO 2 solution, 0.45 ml zirconium n-butoxide was added therein and stirred for 4 hours. The liquid phase with dispersion was replaced by water. Then, the solids were obtained by calcining at 900 °C.
- step (c) The Pd-SiO 2 -ZrO 2 particles obtained in step (c) were stirred in 50 ml solution containing 1 mole sodium hydroxide (NaOH) for 3 hours, then centrifuged and washed with a solution containing 1 mole NaOH. Finally, Pd-ZrO 2 was obtained after drying at room temperature.
- NaOH sodium hydroxide
- the catalyst was placed in a reactor having a mixed atmosphere of hydrogen and nitrogen with a flow rate at 10 ml/min and 40 ml/min, and the benzene was fed with a flow rate at 0.5 ml/hrs.
- the conversion of benzene was 63% when the reaction temperature was 84 °C.
- the noble metals of the abovementioned hydrogenation catalysts are mounted onto aluminum oxide (Al 2 O 3 ) or silica (SiO 2 ), and the catalysts need to be separated from the required product by filtration after the reaction. It is difficult to recover the catalyst when the particles are too small to filter. Furthermore, since platinum is a very rare and expensive metal catalyst for general chemical reactions, the recovery of noble metal catalysts and recovery efficiency are important for reducing process costs to enhance efficiency and save resources.
- US2012/0614034 discloses a hydrogenation catalyst comprising nickel wire with an alumite cladding.
- the support is impregnated with platinum.
- a primary object of the present invention is to provide a hydrogenation catalyst including nickel nanowires which has a high specific surface area.
- noble metal nanoparticles are introduced to improve the catalytic performance of the hydrogenation catalyst.
- the hydrogenation catalyst can be recovered easily by its magnetism to solve the problem of traditional nanocatalysts, which are difficult to reuse, and greatly reduces material costs.
- the secondary object of the present invention is to provide a method of manufacturing a hydrogenation catalyst.
- the nanocrystalline nickel is self-assembled to form one-dimensional nanowires in a simple magnetic field accompanying with electroless plating to produce a magnetic carrier.
- noble metal nanoparticles grow on nickel by additional reducing agents or different an oxidization/reduction potential between two metals themselves without additional reducing agents.
- the method of manufacturing the hydrogenation catalyst is simple, and does not require complex pretreatment, and therefore production costs can be reduced.
- the present invention provides a hydrogenation catalyst, comprising a nanonickel carrier; and noble metal nanoparticles selected from palladium, platinum, ruthenium, rhodium, or a mixture thereof, wherein the noble metal nanoparticles are mounted onto the nanonickel carrier, in accordance with claim 1.
- the nanonickel carrier is constituted by one-dimensional nickel nanowires.
- a specific surface area of the nanonickel carrier is greater than or equal to 0.2 m 2 /g.
- a weight percentage of the noble metal nanoparticles in the hydrogenation catalyst is 2.5-7%.
- an atomic percentage of the noble metal nanoparticles in the hydrogenation catalyst is 1.5-2.5%.
- a specific surface area of the hydrogenation catalyst is greater than or equal to 3.0 m 2 /g.
- the present invention provides a method of manufacturing a hydrogenation catalyst, comprising the steps of: (1) preparing an aqueous solution containing nickel ions; (2) adding a first reducing agent in the aqueous solution containing nickel ions to form a reactant solution; (3) applying a magnetic field to the reactant solution for a first duration to obtain a nanonickel carrier; (4) preparing a noble metal solution containing noble metal ions selected from palladium ions, platinum ions, ruthenium ions, rhodium ions, or a mixture thereof; and (5) placing the nanonickel carrier in the noble metal solution for a second duration so that noble metal nanoparticles are mounted onto the nanonickel carrier, in accordance with claim 5.
- the aqueous solution containing nickel ions in the step (1) is prepared from nickel chloride and deionized water.
- the aqueous solution containing nickel ions further comprises an assistant agent selected from carboxymethyl cellulose (CMC), sodium citrate, sodium hydroxide, or a mixture thereof.
- CMC carboxymethyl cellulose
- sodium citrate sodium citrate
- sodium hydroxide sodium hydroxide
- carboxymethyl cellulose is 4-6% by weight in the aqueous solution containing nickel ions.
- the step (1) further comprises a step (1a) of: heating and stirring until the assistant agent is totally dissolved in the aqueous solution containing nickel ions.
- the first reducing agent is hydrazine.
- the magnetic field is 500-5000 G (Gauss).
- the first duration is 1-3 hours.
- the noble metal solution containing noble metal ions in the step (4) is prepared from a noble metal salt and hydrochloric acid.
- the concentration of the hydrochloric acid is 10 N (mole/Kg).
- the noble metal solution containing noble metal ions further comprises an additive selected from sodium citrate, sodium hydroxide, or a mixture thereof.
- the step (4) further comprises a step (4a) of: heating and stirring until the additive is totally dissolved in the aqueous solution containing noble metal ions.
- the step (5) further comprises a step of adding a second reducing agent to facilitate the formation of the noble metal nanoparticles.
- the second reducing agent is hydrazine.
- the second duration is 1-3 hours.
- a hydrogenation catalyst is provided according to one embodiment of the present invention, which comprises a carrier made of nano nickel, constituted by one-dimensional nanowires, and noble metal nanoparticles selected from palladium (Pd), platinum (Pt), ruthenium (Ru), Rhodium (Rh), or a mixture thereof.
- the noble metal nanoparticles connect to at least a portion of the surface of the nanonickel carrier.
- the noble metal nanoparticles are capable of catalyzing hydrogenation reactions, and therefore unsaturated bonds in carbon chains (mainly double bonds between two carbon atoms) are converted to saturated carbon-to-carbon bonds.
- the nanonickel carrier constituted by one-dimensional nickel nanowires has a specific surface area greater than or equal to 0.29 m 2 /g, for example 0.30 m 2 /g, 0.32 m 2 /g, or 0.35 m 2 /g, but it is not limited thereto.
- a weight percentage of the noble metal nanoparticles in the hydrogenation catalyst is 2.5-7%, for example 2.9%, 3.5%, or 6.4%, but it is not limited thereto.
- an atomic percentage of the noble metal nanoparticles in the hydrogenation catalyst is 1.5-2.5%, for example 1.6%, 2.1%, or 2.3%, but it is not limited thereto.
- a specific surface area of the hydrogenation catalyst is greater than or equal to 3.0 m 2 /g.
- the hydrogenation catalyst has a high specific surface area in a range of 3.5-4.5 m 2 /g, for example, 3.7 m 2 /g or 4.3 m 2 /g, but it is not limited thereto.
- a method of manufacturing a hydrogenation catalyst according to one embodiment of the present invention, and mainly comprises the steps of (S1) preparing an aqueous solution containing nickel ions; (S2) adding a first reducing agent in the aqueous solution containing nickel ions to form a reactant solution; (S3) applying a magnetic field to the reactant solution for a first duration to obtain a nanonickel carrier; (S4) preparing a noble metal solution containing noble metal ions selected from palladium ions, platinum ions, ruthenium ions, rhodium ions, or a mixture thereof; and (S5) placing the nanonickel carrier in the noble metal solution for a second duration so that noble metal nanoparticles are mounted onto the nanonickel carrier.
- S1 preparing an aqueous solution containing nickel ions
- S2 adding a first reducing agent in the aqueous solution containing nickel ions to form a reactant solution
- S3 applying a magnetic field to the reactant solution for a first duration to obtain
- the method of manufacturing a hydrogenation catalyst is the step (S1): preparing an aqueous solution containing nickel ions.
- the aqueous solution containing nickel ions can be prepared from nickel salts and deionized water.
- the nickel salts may be, for example, nickel chloride, nickel nitrate, or nickel hydroxide.
- the aqueous solution containing nickel ions further comprises an assistant agent selected from carboxymethyl cellulose (CMC), sodium citrate, sodium hydroxide, or a mixture thereof.
- the amount of the added CMC in the aqueous solution containing nickel ions is 4 to 6% by weight, for example 4.5%, 5%, or 6%, but it is not limited thereto.
- the amount of the added sodium citrate in the aqueous solution containing nickel ions is 5-9%.
- the amount of the added sodium hydroxide in the aqueous solution containing nickel ions is 0.5-2% by weight.
- the method of manufacturing a hydrogenation catalyst according to one embodiment of the present invention is the step (S2): adding a first reducing agent in the aqueous solution containing nickel ions to form a reactant solution.
- the first reducing agent is hydrazine or hydrogen peroxide, for example.
- the weight percentage of the added first reducing agent in the aqueous solution containing nickel ions is 3-9%, for example 3%, 6% or 9%, but it is not limited thereto.
- the method of manufacturing a hydrogenation catalyst according to one embodiment of the present invention is the step (S3): applying a magnetic field to the reactant solution for a first duration to obtain a nanonickel carrier.
- the magnetic field is 500-5000 G.
- the first duration is 1-3 hours, for example 1, 1.5, or 2.5 hours, but it is not limited thereto.
- the method of manufacturing a hydrogenation catalyst according to one embodiment of the present invention is the step (S4): preparing a noble metal solution containing noble metal ions selected from palladium ions, platinum ions, ruthenium ions, rhodium ions, or a mixture thereof.
- the noble metal solution containing noble metal ions can be prepared by noble metal salts and hydrochloric acid (HCI).
- the noble metal salts may be, for example, palladium chloride, palladium bromide, palladium nitrate, or dihydrogen hexachloroplatinate (IV) hexahydrate.
- the concentration of the hydrochloric acid may be, for example, 10N (Molality, mole/Kg), but it is not limited thereto.
- the noble metal solution containing noble metal ions may further contain an additive selected from sodium citrate, sodium hydroxide, or a mixture thereof.
- the amount of the added sodium citrate in the noble metal solution containing noble metal ions is 5-9%.
- the amount of the added sodium hydroxide in the noble metal solution containing noble metal ions is 0.5-2% by weight. If the additive is a solid, a further step of (S4a): heating and stirring until the additive is totally dissolved in the noble metal solution containing noble metal ions, is preferably adopted.
- the method of manufacturing a hydrogenation catalyst is the step (S5): placing the nanonickel carrier in the noble metal solution for a second duration so that noble metal nanoparticles are mounted onto the nanonickel carrier.
- the noble metal nanoparticles are formed by reducing the noble metal ions through the nanonickel carrier (i.e., the different oxidization/reduction potential between two metals themselves can be used without additional reducing agents to achieve the reduction of the noble metal ions, but the reaction is slower), or by adding a second reducing agent in the noble metal solution containing noble metal ions to accelerate the formation of the noble metal nanoparticles.
- the second reducing agent is hydrazine or hydrogen peroxide, for example.
- the weight percentage of the added second reducing agent in the noble metal solution containing noble metal ions is 3-9%, for example 3%, 6%, or 9%, but it is not limited thereto.
- the second duration is 1-3 hours, for example 1, 1.5 or 2.5 hours, but it is not limited thereto.
- preparing the nanonickel carrier by the following steps: Using 1.2 g of nickel chloride and 50 ml of deionized water to form an aqueous solution, and then 2.5 g of carboxymethyl cellulose (CMC) is added therein. The amount of the added CMC in the total weight is about 5%. Next, 3.5 g of sodium citrate and 0.4 g of sodium hydroxide are sequentially added in the aqueous solution, and the aqueous solution is stirred at 80°C to completely dissolve the solids therein. Next, 2 ml of hydrazine is added to form a mixture (a). A fixed magnetic field is applied to the mixture (a), and a reduction reaction is performed for 2 hours.
- CMC carboxymethyl cellulose
- Figs. 1a-1c show the nickel nanowires observed by SEM.
- a specific surface area calculated by BET method of the nickel nanowires is around 0.298 m 2 /g (i.e., Adsorption theory proposed by Stephen Brunauer, Paul Hugh Emmett, and Edward Teller, referred hereafter as BET).
- platinum nanoparticles are grown on the nickel nanowires to form a Pt/Ni hydrogenation catalyst, and the steps thereof are as below.
- the Pt/Ni hydrogenation catalyst is stored in acetone solvent before use.
- Fig. 2a shows the Pt/Ni hydrogenation catalyst observed by SEM.
- a specific surface area calculated by BET method of the Pt/Ni hydrogenation catalyst is around 4.36 m 2 /g.
- the weight percentage of the platinum nanoparticles in the Pt/Ni hydrogenation catalyst is 6.4%
- the atomic percentage of the platinum nanoparticles in the Pt/Ni hydrogenation catalyst is 2.02%.
- platinum nanoparticles could be replaced by palladium (Pd) nanoparticles on the nickel nanowires to produce a Pd/Ni hydrogenation catalyst, and the steps thereof are as below.
- Fig. 2b shows the Pt/Ni hydrogenation catalyst observed by SEM.
- a specific surface area calculated by BET method of the Pd/Ni hydrogenation catalyst is 3.77 m 2 /g.
- the weight percentage of the palladium nanoparticles in the Pd/Ni hydrogenation catalyst is 2.93%, the atomic percentage of the palladium nanoparticles in the Pd/Ni hydrogenation catalyst is 1.64%.
- Fig. 3 shows the catalytic efficiency of Pd/Ni in the hydrogenation of toluene under different pressure of hydrogen atmosphere.
- the hydrogenation reaction of toluene is as shown below:
- the hydrogenated product was sampled at different times during the reaction, and analyzed by gas chromatography (GC) to obtain a real time conversion.
- GC gas chromatography
- the reaction vessel was purged with nitrogen (at a pressure ranged from 30 to 40) for 10-15 minutes to remove remaining hydrogen in the reaction vessel.
- the catalyst was separated from the product by a powerful magnet, and the recovery of the catalyst was over 96%.
- toluene is catalyzed by the Pd/Ni hydrogenation catalyst to form methyl cyclohexane.
- the reaction was carried out at 180 °C under 70 Kg/cm 2 of hydrogen pressure, toluene was completely converted into methyl cyclohexane during reacting for 100 minutes.
- toluene was also completely hydrogenated during reacting for 150 minutes.
- pure nickel nanowires as a hydrogenation catalyst, the hydrogenation reaction has almost no progress.
- Fig. 4 shows a gas chromatography (GC) spectrum of the product obtained from hydrogenation of dimethyl terephthalate (DMT) with the Pd/Ni hydrogenation catalyst according to one embodiment of the present invention.
- the hydrogenation reaction of DMT is as below.
- the remaining steps and reaction conditions were the same as the abovementioned hydrogenation reaction of toluene except that the reactants were 7.5 g DMT and 42.5 g ethyl acetate, the hydrogen pressure was 60 Kg/cm 2 , and the reaction temperature was 200°C. After the reaction was carried out for 180 minutes, the hydrogenation rate was 90%, the purity was 97.36%, and the recovery of the catalyst was over 96%.
- Fig. 5 shows a gas chromatography (GC) spectrum of the product obtained from hydrogenation of dioctyl phthalate (DOP) with the Pd/Ni hydrogenation catalyst according to one embodiment of the present invention.
- the hydrogenation reaction of DOP is as below.
- the hydrogenation catalyst and the method of manufacturing a hydrogenation catalyst in accordance with the present invention introduce the noble metal nanoparticles to improve the catalytic performance of the hydrogenation catalyst.
- the hydrogenation catalyst can be easily recovered by magnetism to solve the problem of a nanocatalyst which is difficult to reuse, and greatly reduces material costs.
- the process of manufacturing the hydrogenation catalyst is simple, and does not require complex pretreatment, and therefore the production cost can be reduced.
Description
- The present invention relates to a hydrogenation catalyst and a method of manufacturing the hydrogen catalyst, and more particularly to a hydrogenation catalyst with magnetism and a method of manufacturing the same.
- In general, metal catalysts are frequently used in the hydrogenation system of aromatic compounds. Compared with other catalytic reactions using non-metallic catalysts, metal catalysts are not only clean but also have a low impact on the economy and the environment. In addition, noble metals such as palladium, ruthenium, rhodium, and platinum have been demonstrated to have high catalytic activities in a hydrogen atmosphere.
- For example, the United States Patent No.
6,841,626B1 published on 2005 for Bayer Corporation disclosed that a noble metal, such as platinum (Pt) and palladium (Pd), is used as a catalyst, SiO2 and Al2O3 as a catalyst carrier, and cyclohexane as a solvent to carry out the hydrogenation reaction of polystyrene. The hydrogenation reaction of polystyrene catalyzed by Pt/SiO2 catalyst at a pressure of 875 bar, and a temperature of 150 °C can obtain a hydrogenation rate of 98.4%. While the hydrogenation reaction of polystyrene catalyzed by Pd/Al2O3, a hydrogenation rate approaches 100% under a pressure of 100 bar at a temperature of 200 °C. - In addition, the China Patent No.
101815575 issued on 2010 for Bayer Corporation mentioned that the catalyst used in the gas phase reaction can catalyze the hydrogenation of nitrobenzene to become aniline. The method includes steps of mixing 106.4 mg palladium chloride (PdCl2), 6 ml hydrochloric acid (HCl), and 294 ml distilled water to obtain 300 ml palladium chloride acid (H2PdCl4). In step (a), the mixed solution of 15 ml H2PdCl4 and 31.5 ml water and 3.5 ml methanol was added 33.25 mg polyvinylpyrrolidone - (PVP-40), refluxed at 80 °C for 3 hours. Next, in step (b), 0.6 ml tetraethoxysilane (TEOS) was mixed with 7 ml ethanol. Subsequently, the mixed solution in step (a) was stirred violently, and a mixture of ethanol-ammonia (NH3) was added therein, then the mixture of ethanol-TEOS was quickly added therein, too. After stirring overnight at room temperature, the precipitation was washed with ethanol, and Pd-SiO2 nanoparticles were obtained by centrifugation. In step (c), 0.43 g alcohol-polyethylene glycol ether (such as Marlipal) was dissolved in water to prepare an aqueous solution of Marlipal. Next, the Pd-SiO2 nanoparticles obtained in step (b) were dispersed in 40 g ethanol and heated to 30 °C. Subsequently, the aqueous solution of Marlipal was added to 30 °C Pd-SiO2 solution, 0.45 ml zirconium n-butoxide was added therein and stirred for 4 hours. The liquid phase with dispersion was replaced by water. Then, the solids were obtained by calcining at 900 °C. The Pd-SiO2-ZrO2 particles obtained in step (c) were stirred in 50 ml solution containing 1 mole sodium hydroxide (NaOH) for 3 hours, then centrifuged and washed with a solution containing 1 mole NaOH. Finally, Pd-ZrO2 was obtained after drying at room temperature.
- Furthermore, the Chinese Patent No.
CN101289365 published on 2011 for Zhu et al. taught that 0.12 g nitrate tetra-ammine platinum (Pt(NH3)4(NO3)2) and 7.4 g hexahydrate cobalt nitrate (Co(NO3)2 · 6H2O) were dissolved in 200 ml deionized water, and 3.5 g of the SiO2 carrier was added. After stirring for 2 hours, the mixture is dried in a water bath at 95 °C, and then calcined at 550 °C to obtain a catalyst. The catalyst was placed in a reactor having a mixed atmosphere of hydrogen and nitrogen with a flow rate at 10 ml/min and 40 ml/min, and the benzene was fed with a flow rate at 0.5 ml/hrs. The conversion of benzene was 63% when the reaction temperature was 84 °C. - However, the noble metals of the abovementioned hydrogenation catalysts are mounted onto aluminum oxide (Al2O3) or silica (SiO2), and the catalysts need to be separated from the required product by filtration after the reaction. It is difficult to recover the catalyst when the particles are too small to filter. Furthermore, since platinum is a very rare and expensive metal catalyst for general chemical reactions, the recovery of noble metal catalysts and recovery efficiency are important for reducing process costs to enhance efficiency and save resources.
-
US2012/0614034 discloses a hydrogenation catalyst comprising nickel wire with an alumite cladding. The support is impregnated with platinum. - It is therefore necessary to provide a hydrogenation catalyst and a method of manufacturing the hydrogenation catalyst capable of being recovered easily, in order to solve the problems existing in the conventional technology as described above.
- A primary object of the present invention is to provide a hydrogenation catalyst including nickel nanowires which has a high specific surface area. In addition, noble metal nanoparticles are introduced to improve the catalytic performance of the hydrogenation catalyst. When using a hydrogenation catalyst with magnetism in petrochemicals, polymers, or special high-value chemicals production, the hydrogenation catalyst can be recovered easily by its magnetism to solve the problem of traditional nanocatalysts, which are difficult to reuse, and greatly reduces material costs.
- The secondary object of the present invention is to provide a method of manufacturing a hydrogenation catalyst. First, by referring to a chemical reduction reaction, the nanocrystalline nickel is self-assembled to form one-dimensional nanowires in a simple magnetic field accompanying with electroless plating to produce a magnetic carrier. Subsequently, noble metal nanoparticles grow on nickel by additional reducing agents or different an oxidization/reduction potential between two metals themselves without additional reducing agents. The method of manufacturing the hydrogenation catalyst is simple, and does not require complex pretreatment, and therefore production costs can be reduced.
- To achieve the above objects, the present invention provides a hydrogenation catalyst, comprising a nanonickel carrier; and noble metal nanoparticles selected from palladium, platinum, ruthenium, rhodium, or a mixture thereof, wherein the noble metal nanoparticles are mounted onto the nanonickel carrier, in accordance with claim 1.
- The nanonickel carrier is constituted by one-dimensional nickel nanowires.
- In one embodiment of the present invention, a specific surface area of the nanonickel carrier is greater than or equal to 0.2 m2/g.
- In one embodiment of the present invention, a weight percentage of the noble metal nanoparticles in the hydrogenation catalyst is 2.5-7%.
- In one embodiment of the present invention, an atomic percentage of the noble metal nanoparticles in the hydrogenation catalyst is 1.5-2.5%.
- In one embodiment of the present invention, a specific surface area of the hydrogenation catalyst is greater than or equal to 3.0 m2/g.
- Furthermore, the present invention provides a method of manufacturing a hydrogenation catalyst, comprising the steps of: (1) preparing an aqueous solution containing nickel ions; (2) adding a first reducing agent in the aqueous solution containing nickel ions to form a reactant solution; (3) applying a magnetic field to the reactant solution for a first duration to obtain a nanonickel carrier; (4) preparing a noble metal solution containing noble metal ions selected from palladium ions, platinum ions, ruthenium ions, rhodium ions, or a mixture thereof; and (5) placing the nanonickel carrier in the noble metal solution for a second duration so that noble metal nanoparticles are mounted onto the nanonickel carrier, in accordance with
claim 5. - In one embodiment of the present invention, the aqueous solution containing nickel ions in the step (1) is prepared from nickel chloride and deionized water.
- In one embodiment of the present invention, the aqueous solution containing nickel ions further comprises an assistant agent selected from carboxymethyl cellulose (CMC), sodium citrate, sodium hydroxide, or a mixture thereof.
- In one embodiment of the present invention, carboxymethyl cellulose is 4-6% by weight in the aqueous solution containing nickel ions.
- In one embodiment of the present invention, the step (1) further comprises a step (1a) of: heating and stirring until the assistant agent is totally dissolved in the aqueous solution containing nickel ions.
- In one embodiment of the present invention, the first reducing agent is hydrazine.
- In one embodiment of the present invention, the magnetic field is 500-5000 G (Gauss).
- In one embodiment of the present invention, the first duration is 1-3 hours.
- In one embodiment of the present invention, the noble metal solution containing noble metal ions in the step (4) is prepared from a noble metal salt and hydrochloric acid.
- In one embodiment of the present invention, the concentration of the hydrochloric acid is 10 N (mole/Kg).
- In one embodiment of the present invention, the noble metal solution containing noble metal ions further comprises an additive selected from sodium citrate, sodium hydroxide, or a mixture thereof.
- In one embodiment of the present invention, the step (4) further comprises a step (4a) of: heating and stirring until the additive is totally dissolved in the aqueous solution containing noble metal ions.
- In one embodiment of the present invention, the step (5) further comprises a step of adding a second reducing agent to facilitate the formation of the noble metal nanoparticles.
- In one embodiment of the present invention, the second reducing agent is hydrazine.
- In one embodiment of the present invention, the second duration is 1-3 hours.
-
-
Figs. 1a to 1c are views of the scanning electron microscope (SEM) observation of the nanowires prepared according to one embodiment of the present invention (10kV, by 10kX, 50kX, 100kX). -
Figs. 2a to 2b are views of the SEM observation of the hydrogenation catalyst according to one embodiment of the present invention (10kV, 1,000X-100,000X), whereFig. 2a shows platinum on nickel nanowires (respectively by 1k, 30k, 50k, 100kX from right to left, and from bottom to top),Fig. 2b shows palladium on nickel nanowires (respectively by 1k, 30k, 50k, 100kX from right to left, and from bottom to top). -
Fig. 3 shows the catalytic efficiency of Pd/Ni in the hydrogenation of toluene under different pressures of a hydrogen atmosphere. (■: 70Kg; ●: 50Kg; ∇: 70Kg with pure Ni nanowire as a control group) -
Fig. 4 is a gas chromatography (GC) spectrum of the product obtained from hydrogenation of dimethyl terephthalate (DMT) with the hydrogenation catalyst according to one embodiment of the present invention. -
Fig. 5 is a GC spectrum of the product obtained from hydrogenation of dioctyl phthalate (DOP) with the hydrogenation catalyst according to one embodiment of the present invention. - The structure and the technical means adopted by the present invention to achieve the above and other objects can be best understood by referring to the following detailed description of the preferred embodiments and the accompanying drawings. Furthermore, if there is no specific description in the invention, singular terms such as "a", "one", and "the" include the plural number. For example, "a compound" or "at least one compound" may include a plurality of compounds, and the mixtures thereof. If there is no specific description in the invention, the "%" means "weight percent (wt%)", and the numerical range (e.g. 10%-11% of A) contains the upper and lower limit (i.e. 10%≦A≦11%). If the lower limit is not defined in the range (e.g. less than, or below 0.2% of B), it means that the lower limit is 0 (i.e. 0%≦B≦0.2%). The proportion of "weight percent" of each component can be replaced by the proportion of "weight portion" thereof. The abovementioned terms are used to describe and understand the present invention, but the present invention is not limited thereto.
- A hydrogenation catalyst is provided according to one embodiment of the present invention, which comprises a carrier made of nano nickel, constituted by one-dimensional nanowires, and noble metal nanoparticles selected from palladium (Pd), platinum (Pt), ruthenium (Ru), Rhodium (Rh), or a mixture thereof. The noble metal nanoparticles connect to at least a portion of the surface of the nanonickel carrier. The noble metal nanoparticles are capable of catalyzing hydrogenation reactions, and therefore unsaturated bonds in carbon chains (mainly double bonds between two carbon atoms) are converted to saturated carbon-to-carbon bonds. The nanonickel carrier constituted by one-dimensional nickel nanowires has a specific surface area greater than or equal to 0.29 m2/g, for example 0.30 m2/g, 0.32 m2/g, or 0.35 m2/g, but it is not limited thereto. Preferably, a weight percentage of the noble metal nanoparticles in the hydrogenation catalyst is 2.5-7%, for example 2.9%, 3.5%, or 6.4%, but it is not limited thereto. Preferably, an atomic percentage of the noble metal nanoparticles in the hydrogenation catalyst is 1.5-2.5%, for example 1.6%, 2.1%, or 2.3%, but it is not limited thereto. In addition, a specific surface area of the hydrogenation catalyst is greater than or equal to 3.0 m2/g. Preferably, the hydrogenation catalyst has a high specific surface area in a range of 3.5-4.5 m2/g, for example, 3.7 m2/g or 4.3 m2/g, but it is not limited thereto.
- Furthermore, a method of manufacturing a hydrogenation catalyst according to one embodiment of the present invention is provided, and mainly comprises the steps of (S1) preparing an aqueous solution containing nickel ions; (S2) adding a first reducing agent in the aqueous solution containing nickel ions to form a reactant solution; (S3) applying a magnetic field to the reactant solution for a first duration to obtain a nanonickel carrier; (S4) preparing a noble metal solution containing noble metal ions selected from palladium ions, platinum ions, ruthenium ions, rhodium ions, or a mixture thereof; and (S5) placing the nanonickel carrier in the noble metal solution for a second duration so that noble metal nanoparticles are mounted onto the nanonickel carrier. The principle and the implementation details of each step in this embodiment of the present invention will be described in detail hereinafter.
- First, the method of manufacturing a hydrogenation catalyst according to a preferred embodiment of the present invention is the step (S1): preparing an aqueous solution containing nickel ions. In this step, the aqueous solution containing nickel ions can be prepared from nickel salts and deionized water. The nickel salts may be, for example, nickel chloride, nickel nitrate, or nickel hydroxide. The aqueous solution containing nickel ions further comprises an assistant agent selected from carboxymethyl cellulose (CMC), sodium citrate, sodium hydroxide, or a mixture thereof. The amount of the added CMC in the aqueous solution containing nickel ions is 4 to 6% by weight, for example 4.5%, 5%, or 6%, but it is not limited thereto. The amount of the added sodium citrate in the aqueous solution containing nickel ions is 5-9%. The amount of the added sodium hydroxide in the aqueous solution containing nickel ions is 0.5-2% by weight. If the assistant agent is a solid, a further step of (S1a): heating and stirring until the assistant agent is totally dissolved in the aqueous solution containing nickel ions, is preferably adopted.
- Next, the method of manufacturing a hydrogenation catalyst according to one embodiment of the present invention is the step (S2): adding a first reducing agent in the aqueous solution containing nickel ions to form a reactant solution. In this step, the first reducing agent is hydrazine or hydrogen peroxide, for example. In addition, the weight percentage of the added first reducing agent in the aqueous solution containing nickel ions is 3-9%, for example 3%, 6% or 9%, but it is not limited thereto.
- Next, the method of manufacturing a hydrogenation catalyst according to one embodiment of the present invention is the step (S3): applying a magnetic field to the reactant solution for a first duration to obtain a nanonickel carrier. In this step, the magnetic field is 500-5000 G. The first duration is 1-3 hours, for example 1, 1.5, or 2.5 hours, but it is not limited thereto.
- Next, the method of manufacturing a hydrogenation catalyst according to one embodiment of the present invention is the step (S4): preparing a noble metal solution containing noble metal ions selected from palladium ions, platinum ions, ruthenium ions, rhodium ions, or a mixture thereof. In this step, the noble metal solution containing noble metal ions can be prepared by noble metal salts and hydrochloric acid (HCI). The noble metal salts may be, for example, palladium chloride, palladium bromide, palladium nitrate, or dihydrogen hexachloroplatinate (IV) hexahydrate. The concentration of the hydrochloric acid may be, for example, 10N (Molality, mole/Kg), but it is not limited thereto. The noble metal solution containing noble metal ions may further contain an additive selected from sodium citrate, sodium hydroxide, or a mixture thereof. The amount of the added sodium citrate in the noble metal solution containing noble metal ions is 5-9%. The amount of the added sodium hydroxide in the noble metal solution containing noble metal ions is 0.5-2% by weight. If the additive is a solid, a further step of (S4a): heating and stirring until the additive is totally dissolved in the noble metal solution containing noble metal ions, is preferably adopted.
- Lastly, the method of manufacturing a hydrogenation catalyst according to one embodiment of the present invention is the step (S5): placing the nanonickel carrier in the noble metal solution for a second duration so that noble metal nanoparticles are mounted onto the nanonickel carrier. In this step, the noble metal nanoparticles are formed by reducing the noble metal ions through the nanonickel carrier (i.e., the different oxidization/reduction potential between two metals themselves can be used without additional reducing agents to achieve the reduction of the noble metal ions, but the reaction is slower), or by adding a second reducing agent in the noble metal solution containing noble metal ions to accelerate the formation of the noble metal nanoparticles. The second reducing agent is hydrazine or hydrogen peroxide, for example. In addition, the weight percentage of the added second reducing agent in the noble metal solution containing noble metal ions is 3-9%, for example 3%, 6%, or 9%, but it is not limited thereto. The second duration is 1-3 hours, for example 1, 1.5 or 2.5 hours, but it is not limited thereto.
- To make the hydrogenation catalyst and the method for manufacturing the hydrogenation catalyst of the present invention more definite, please refer to the actual manufacturing process described in the following. The exemplified preparation of the catalyst is not used to restrict to the composition and the manufacturing method thereof.
- In a preferred embodiment of the invention, first, preparing the nanonickel carrier by the following steps:
Using 1.2 g of nickel chloride and 50 ml of deionized water to form an aqueous solution, and then 2.5 g of carboxymethyl cellulose (CMC) is added therein. The amount of the added CMC in the total weight is about 5%. Next, 3.5 g of sodium citrate and 0.4 g of sodium hydroxide are sequentially added in the aqueous solution, and the aqueous solution is stirred at 80°C to completely dissolve the solids therein. Next, 2 ml of hydrazine is added to form a mixture (a). A fixed magnetic field is applied to the mixture (a), and a reduction reaction is performed for 2 hours. After the reaction is finished, the product is washed by 70°C deionized water for removing CMC, and the nickel nanowires are obtained. The nickel nanowires are stored in ethanol before use.Figs. 1a-1c show the nickel nanowires observed by SEM. A specific surface area calculated by BET method of the nickel nanowires is around 0.298 m2/g (i.e., Adsorption theory proposed by Stephen Brunauer, Paul Hugh Emmett, and Edward Teller, referred hereafter as BET). - Next, platinum nanoparticles are grown on the nickel nanowires to form a Pt/Ni hydrogenation catalyst, and the steps thereof are as below.
- Preparing an aqueous solution of dihydrogen hexachloroplatinate (IV) hexahydrate (H2PtCl6·(H2O)6) containing 0.4g platinum ions per 100 ml, for example, 0.03 g dihydrogen hexachloroplatinate (IV) hexahydrate is dissolved in 7.5 ml of deionized water at 70°C. Then, 0.5g Na3C6H5O7 (sodium citrate), 0.4g NaOH (sodium hydroxide), and 20 ml deionized water are added in 7.5 ml of the aqueous solution of dihydrogen hexachloroplatinate (IV) hexahydrate, and stirred at 60 °C until the added solids are dissolved to obtain a mixture (b). 1g nickel nanowires are placed into the mixture (b), and 12 ml of N2H4 (Hydrazine) is added therein as a reducing agent. After 2 hours, the precipitation is washed by 70°C deionized water several times to purify the Pt/Ni hydrogenation catalyst. The Pt/Ni hydrogenation catalyst is stored in acetone solvent before use.
Fig. 2a shows the Pt/Ni hydrogenation catalyst observed by SEM. In addition, a specific surface area calculated by BET method of the Pt/Ni hydrogenation catalyst is around 4.36 m2/g. The weight percentage of the platinum nanoparticles in the Pt/Ni hydrogenation catalyst is 6.4%, the atomic percentage of the platinum nanoparticles in the Pt/Ni hydrogenation catalyst is 2.02%. - Alternatively, the platinum nanoparticles could be replaced by palladium (Pd) nanoparticles on the nickel nanowires to produce a Pd/Ni hydrogenation catalyst, and the steps thereof are as below.
- Preparing 100 ml of 10 N HCI, and adding 1.77 g of palladium chloride in the hydrochloric acid solution, then stirring at 70°C until the added solids are dissolved to form an aqueous solution of palladium chloride. Next, 3 g of sodium citrate and 2.4 g of sodium hydroxide are added in 180 ml of the aqueous solution of palladium chloride, and stirred at 60°C until they are dissolved to form a mixture (c). 1 g nickel nanowires are placed into the mixture (c), and 12 ml of N2H4 (Hydrazine) is added therein as a reducing agent. After 2 hours, the precipitation is washed by 70°C deionized water several times to purify the Pd/Ni hydrogenation catalyst. The Pd/Ni hydrogenation catalyst is stored in an acetone solvent before use.
Fig. 2b shows the Pt/Ni hydrogenation catalyst observed by SEM. In addition, a specific surface area calculated by BET method of the Pd/Ni hydrogenation catalyst is 3.77 m2/g. The weight percentage of the palladium nanoparticles in the Pd/Ni hydrogenation catalyst is 2.93%, the atomic percentage of the palladium nanoparticles in the Pd/Ni hydrogenation catalyst is 1.64%. - In order to verify the hydrogenation efficiency of the hydrogenation catalyst according to the present invention, the following experiments and analysis of the hydrogenated products are carried out.
-
- First, 50 g toluene was placed into a reaction vessel, and then Pd/Ni hydrogenation catalyst or pure nickel wire (control group) with an amount by 5 wt% of toluene was added. The foregoing mixture were stirred at 1000 rpm, and purged with nitrogen (at a pressure ranged from 30 to 40 psi) for 10-15 minutes to remove oxygen in the reaction vessel. After purged with nitrogen, the reaction vessel was purged with hydrogen (at a pressure ranged from 30 to 40 psi) for 10-15 minutes to remove nitrogen in the reaction vessel. Subsequently, the hydrogen pressure was set to 70, or 50 Kg/cm2; the reaction temperature was at 180 °C. The hydrogenated product was sampled at different times during the reaction, and analyzed by gas chromatography (GC) to obtain a real time conversion. After the reaction has been completed, the reaction vessel was purged with nitrogen (at a pressure ranged from 30 to 40) for 10-15 minutes to remove remaining hydrogen in the reaction vessel. Subsequently, the catalyst was separated from the product by a powerful magnet, and the recovery of the catalyst was over 96%.
- From
Fig. 3 , toluene is catalyzed by the Pd/Ni hydrogenation catalyst to form methyl cyclohexane. When the reaction was carried out at 180 °C under 70 Kg/cm2 of hydrogen pressure, toluene was completely converted into methyl cyclohexane during reacting for 100 minutes. When the reaction was carried out at 180°C under 50 Kg/cm2 of hydrogen pressure, toluene was also completely hydrogenated during reacting for 150 minutes. In contrast, when using pure nickel nanowires as a hydrogenation catalyst, the hydrogenation reaction has almost no progress. -
- The remaining steps and reaction conditions were the same as the abovementioned hydrogenation reaction of toluene except that the reactants were 7.5 g DMT and 42.5 g ethyl acetate, the hydrogen pressure was 60 Kg/cm2, and the reaction temperature was 200°C. After the reaction was carried out for 180 minutes, the hydrogenation rate was 90%, the purity was 97.36%, and the recovery of the catalyst was over 96%.
-
- The remaining steps and reaction conditions were the same as the abovementioned hydrogenation reaction of toluene except that the reactants was 50 g DOP, the hydrogen pressure was 60 Kg/cm2, and the reaction temperature was 200°C. After completing the reaction, the hydrogenation rate was 90%, and the recovery of the catalyst was over 96%.
- Furthermore, in the hydrogenation reaction of polystyrene (PS) with Pd/Ni hydrogenation catalyst, the remaining steps and reaction conditions were the same as the abovementioned hydrogenation reaction of toluene except that the reactants were 5 g PS and 45 g cyclohexane, the hydrogen pressure was 200 psi, and the reaction temperature was 80°C. After the reaction was carried out for 30 minutes, the hydrogenation rate was confirmed as more than 80%.
- Compared with conventional techniques, the hydrogenation catalyst and the method of manufacturing a hydrogenation catalyst in accordance with the present invention introduce the noble metal nanoparticles to improve the catalytic performance of the hydrogenation catalyst. In addition, the hydrogenation catalyst can be easily recovered by magnetism to solve the problem of a nanocatalyst which is difficult to reuse, and greatly reduces material costs. Moreover, the process of manufacturing the hydrogenation catalyst is simple, and does not require complex pretreatment, and therefore the production cost can be reduced.
Claims (13)
- A hydrogenation catalyst, comprising:a nanonickel carrier constituted by one-dimensional nickel nanowires; andnoble metal nanoparticles selected from palladium, platinum, ruthenium, rhodium or a mixture thereof,wherein the noble metal nanoparticles are mounted onto the nanonickel carrier.
- The hydrogenation catalyst according to Claim 1, wherein a specific surface area of the nanonickel carrier is greater than or equal to 0.2 m2/g, and a specific surface area of the hydrogenation catalyst is greater than or equal to 3.0 m2/g.
- The hydrogenation catalyst according to Claim 1, wherein a weight percentage of the noble metal nanoparticles in the hydrogenation catalyst is 2.5-7%.
- The hydrogenation catalyst according to Claim 1, wherein an atomic percentage of the noble metal nanoparticles in the hydrogenation catalyst is 1.5-2.5%.
- A method for manufacturing a hydrogenation catalyst, comprising steps of:(1) preparing an aqueous solution containing nickel ions;(2) adding a first reducing agent in the aqueous solution containing nickel ions to form a reactant solution;(3) applying a magnetic field to the reactant solution for a first duration to obtain a nanonickel carrier constituted by one-dimensional nickel nanowires;(4) preparing a noble metal solution containing noble metal ions selected from palladium ions, platinum ions, ruthenium ions, rhodium ions or a mixture thereof; and(5) placing the nanonickel carrier in the noble metal solution for a second duration so that noble metal nanoparticles are mounted onto the nanonickel carrier.
- The method according to Claim 5, wherein the aqueous solution containing nickel ions in the step (1) is prepared from nickel chloride and deionized water.
- The method according to Claim 5, wherein the step (1) further comprises a step (1a) of: heating and stirring until an assistant agent is totally dissolved in the aqueous solution containing nickel ions, and the assistant agent is selected from carboxymethyl cellulose, sodium citrate, sodium hydroxide or a mixture thereof.
- The method according to Claim 7, wherein carboxymethyl cellulose is 4-6% by weight in the aqueous solution containing nickel ions.
- The method according to Claim 5, wherein the first reducing agent is hydrazine.
- The method according to Claim 5, wherein the magnetic field is 500-5000 G, the first duration is 1-3 hours, and the second duration is 1-3 hours.
- The method according to Claim 5, wherein the noble metal solution containing noble metal ions in the step (4) is prepared from a noble metal salt and hydrochloric acid, and the concentration of the hydrochloric acid is 10 N.
- The method according to Claim 5, wherein the step (4) further comprises a step (4a) of: heating and stirring until an additive is totally dissolved in the aqueous solution containing noble metal ions, and the additive is selected from sodium citrate, sodium hydroxide, or a mixture thereof.
- The method according to Claim 5, wherein the step (5) further comprises a step of adding a second reducing agent to facilitate the formation of the noble metal nanoparticles, and the second reducing agent is hydrazine.
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CN108212162B (en) * | 2016-12-22 | 2021-03-16 | 成功大学 | Nano nickel catalyst and hydrogenation method of carbon oxide |
CN109752411B (en) * | 2017-11-07 | 2021-09-17 | 国家纳米科学中心 | Composite gas-sensitive material and preparation method and application thereof |
KR102178389B1 (en) * | 2018-01-15 | 2020-11-12 | 한국과학기술연구원 | Catalyst, catalyst composition comprising pd-ni alloy and methods for synthesizing of hydrogen peroxide using them |
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CN113174599B (en) * | 2021-04-16 | 2022-03-11 | 青岛科技大学 | Nickel-based hierarchical structure integrated electrode for water electrolysis and preparation method thereof |
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